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The Chelate Compounds of Plutonium Frederick John Wolter Iowa State College

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The Chelate Compounds of Plutonium Frederick John Wolter Iowa State College Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1946 The chelate compounds of plutonium Frederick John Wolter Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Physical Chemistry Commons Recommended Citation Wolter, Frederick John, "The chelate compounds of plutonium " (1946). Retrospective Theses and Dissertations. 14179. https://lib.dr.iastate.edu/rtd/14179 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. NOTE TO USERS This reproduction is the best copy available. UMI ras CHSIJ^TE COMPOUNDS OF PLUTONIUM , -3*- by Trederiok Jobn Wolter A ^esis Sttlmitted to the Graduate Faeultj for the Degree of DOOTOfi OF PHILOSOPHY Ifajor Subjeot: Phyeieal Ghoaietry ApproTed: Signature was redacted for privacy. In Gliarge Major Woric Signature was redacted for privacy. Head of Major Departa^t Signature was redacted for privacy. Dean of ^^oate College Zowa State &>Xlege 1946 UMI Number: DP13061 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform DP13061 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 , -1 f; ^ I ^ ' ' TABLE OF CONTENTS Page I IMTRODUGTIOH 1 1.1 History of the Plutonium Problem 1 1.2 The Chemioal Properties of Plutoniisa .... 3 1.2.1 Oxidation etatea ..... 4 1.2*2 Oxidation and reduction of plutoniua . 6 1.2.3 lonie species and complex formation . 10 1.2.4 The position of plutonium in the periodic table 12 1.3 Statement of the Probleoa 15 II THE NATURE OF C3HELATfi C0MP0T3NDB le 2.1 Homenolature 16 2.2 Properties of Chelate Compounds 1? 2.3 Factors InTOlTed in the Formation of Chelate Compounds 19 2.3.1 General conditions for complex for- laatioa 19 2.3.2 The cbemical bonds formed in com­ plex compounds 20 2.3.3 Functional groups in chelating rea­ gents 21 2.3.4 l&e nature of the donor atom 22 2.3.5 The nature of the acceptor atom ... 24 2.3.6 Ring formation 26 2.3.7 The possible oomplexing properties of plutoniiM 28 ill Pag« in ISXPERKSOTAL METHODS ARI3 TSOHMlQimS Z9 3,1 Extractions on the Tracer Scale .... 29 3.a Extractions on the Micro Scale 30 3.3 Radioactive Assays . 3S 3.3.1 Plutonium assays . 32 3.3.2 Other radioactive assays .... 34 IT MATERlikLS USID 36 4.1 Flutoniim 36 4.2 Other Radioactive Isotopes ....... 36 4.3 Solvents ...... 36 4.4 Organic Reagents 37 r THE GHSLATE COKPODNDS OF PLtJTONlUM(IT) 40 5.1 Exploratory Sxperimente on the Tracer Scale ....... 40 5.1.1 Introduction .......... 40 5.1.2 Experiments with bidentate rea­ gents 40 5.1.3 Experiments with quadridentate reagents ...... 45 5.1.4 Discussion 51 5.2 Extended Studies v.'ith Disal ...... 55 5.2.1 Conditions for preparing the Pa(17)-disal complex on the Micro scale 55 5.2.2 The composition of the Pu(IV)- disal complex 57 5.2.3 The use of various solvents for disal extractions ........ 59 IT Pag® 5.2.4 Behavior of the Pa{I?)-disal oomplex toward dilute aoids .... 60 5.2.5 Interfering substanoes , 62 5.2.6 Discussion . 64 5.3 The Plutonium(Hr)-Ferron Complex 69 5.3.1 Introduotion . 67 5.3.2 ipcperimental 69 5.3.3 Disoussion 76 n THE CBLSLATl COMPOUNDS OF PLUTONIUM(III) 78 6.1 Introduotion 78 6.2 Experimental ........ 78 6*2.1 General procedure ......... 78 6.2.2 The behavior of plutonimdll} with hydroxamio aoids 80 6.2.3 The behavior of plutonium(III} with amide oximes 85 6.2.4 ^e behavior of plutoniuia{IlI) with misoellaneous bideatate rea­ gents .... 87 6.3 Discussion 89 711 THB USI OF OHGAKIC REAGENTS FOR THE DICONTMIKA- TION AND PURIFICATION OF PLUTONIUM 95 7.1 Introduotion 93 7.2 Sxperimental . 94 7.2.1 The behavior of various cations with disal . 94 7.2.2 lit tempts to adapt disal extrac­ tions to the separation of Plu­ tonium from zirconium and thorium . 98 • Page 7.2.3 The behavior of various cations with hydroxamlo aoids 100 7.2.4 The behavior of various cations with amide oximes 103 7.3 Discussion 105 VIII SIMIARY 109 IX LITIRATURE OITED 113 X AGKNOWLlDGmENTS 119 -1- I IHTRODUOTION 1.1 History of the Plutoniiim Problem The first transuranium element was discovered in May, 1940 by McMillan and Abelson (1), who found a radioactivity with a 2,3 day half-life formed by irradiation of uranium with neutrons, and emitting negative./-rays. After showing that it differed from uranium and the fission products they identified this activity as the daughter of 23 minuter-ac­ ^39 tive which is formed by the radiative capture of neu­ trons by The new element therefore has an atomic num­ ber one greater than that of uranium and is elem^t 93. Their work on the tracer soale showed that element 93 has at least two oxidation states, and that oxidation to the higher state requires more vigorous conditions than the cor­ responding oxidation of uranium. The new element was giv^ the name neptu.iiur.. The next transuranium eleiaent discovered was elaaent 94. Late in 1940, Seaborg, McMillan, Wahl, and Kennedy (2) identified as element 94 theX-active element formed by the decay of the intermediate neptunium produced by a d, 2a re­ action on 0®®®, -2- ggTr^®®{d,2n)gglip®^ 94238 Slement 94 was aamed plutoaium. ^fae isotope is aa ^-aeitter with a half-life of about 115 years. Early experime&ts with tracer ajoouats of showed that the eloaaent had at least two oxidatioa states» aad that Ibr producing the higher oxidatioa state erea more Tigorous oxi­ dizing agents were required thaa for the oorrespoading op<r eration with neptuaitm, TtkB isotope of plutoaium whioh is of greatest ia^or^ tanoe is the long-lived <K-emitter Pu®®*, the daughter of 2.3 day Np^®®. Ctonsideration of the Bohr-Wheeler theory of fission (3) and of oertain ^pirieal relations among heavy nuclei by L. A. Turner (4) and others had suggested that would be a long-lived X-«aitter and that it might be fissionable be slow neutrons. It had been found by the middle of 1940 that neutrons were knitted in the process of fission of uraniim (5). fhus at that time many of the prerequisites for a serious study of the production of atomic energy were at hand. The dramatic history of the development of the atomic bomb has been described in the now-famous Smyth report C^}* ^9 Metallurgical Project had as its object a method for obtaining large quantities of pure Pa^®. The first aspect of the problaa was the develoxanent of a controllable olMiiii reaotlng struotupe which would produce in a matrix of uraQiim. The second part of the prohim was to leara enough of the chemistry of pXutoniua to derise aa effioiect method of separating the fraai uraniim and highly radioactive fission produots and of produeing in 6 state of purity useful for military purposes, These goals were achieved by a research program i& which many of the chemical studies were done with mioro* scopic and sulmloroBoopio quantities of material. In fact it was not until August of 1942 (7) that the first pure com­ pound of Plutonium free from carrier material and other for­ eign matter was prepared. Milligram quantities did not he* eome available until much later. Since early 1944 investi* gations have been continued with increasingly larger saounts of Plutonium* until plutonium has been brought from the realm of little-icnown elements to a position where its cheeiioal and physical properties are as well or better understood than those of mahy other elements. 1.8 The Ghemical Properties of Plutonium My reasonably complete discussion of the chemical properties of plutonium would require volumes. The pur­ pose of this brief discussion is to summarize a few of the more important properties of plutonium as they apply to a study of the chelate compounds of plutonium. So attempt will be made to aafce specific references to the original project reports In whioh the work was desoribed, as this has been done in the report of Thomas and Warner (6) and will be ooTered oompletely in the forthoomiag volumes of the Plutonium Project Record (9}« 1.2.1 Oxidation states. ffee diposltlTe state. Of the compounds of Pu(II), PuO is the best knotvn. It is readily soluble in dilute HOI with the liberation of hydrogen, so apparently Pu{II) is not stable in acid solution. The dipositive state is produced by aetallic reduction of solid compounds of higher oxidation states* The tripositiTe state. Plutonium(IH) in aqueous solution has a blue to violet color. The absorption spec­ trum of Pu{III) solutions has several absorption bands, some of iirhioh are narrow.
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